CHM 151: FOUNDATION CHEMISTRY II

2nd Semester 2023/2024

Content
Liquids - Pressure and Temperature Relationship. Henry's law. Colligative properties
- Boiling Point Elevation, Freezing Point Depression, and Osmotic Pressure. Raoult's
laws. Azeotropic mixtures.

Liquids
Pressure and Temperature relationship
Introduction
In the study of gases, it can be noted that at high pressure and low temperatures,
volume decreases sharply and intermolecular forces cause gas behaviour to depart
from ideality. When these forces are sufficiently strong, the gas condenses to a liquid.
The intermolecular forces keep the molecules in close enough proximity that the
molecules are confined to a definite volume as expected for the liquid state. Thus,
intermolecular forces are important in establishing the vapour pressure, surface
tension, viscosity, and other related properties of a liquid.

Vapour pressure
Liquids are constantly vaporising. As time passes more and more molecules leave the
liquid surface and come above the liquid surface, thus forming vapours above the
liquid surface.

If the liquid is in a closed vessel with space above it, a partial pressure of the vapour
state builds up in this space. The molecules in the vapour are in the stale of continuous
motion, when some of these molecules strike liquid surface, they are recaptured by it,
this reverse process of vaporisation is called condensation.

Initially the rate of evaporation is very high because more and more molecules of high
energy leave the liquid leaving behind the less energy molecules. But with lime rale of
condensation increases as number of molecules in vapour phase increases. Once the
rale of evaporation and rate of condensation because equal, the concentration of
molecules in vapour remains content and the vapour exerts a constant pressure.
Pressure of vapours in equilibrium with liquid at a given temperature is called its
vapour pressure.

Factors affecting vapour pressure

i. Temperature
The quantity of heat required to evaporate a given liquid at constant temperature is
defined as the heat of vaporisation or enthalpy of vaporisation. Increases in
temperature causes more vaporisation Calculation of heat of vaporisation (∆Hvap)
when vapour pressure at two different temperatures are known, is given by the
Clausius-Clapeyon equation given below.

Page 1 of 15
ii. Nature of liquid
Liquids having strong intermolecular attraction (eg alcohol and water) have less
tendency of evaporation and thus they have low vapour pressure. Alcohols and water
are in associated form due to intermolecular H-bonding.
Liquids having weak intermolecular attraction (as in ether), have more tendency of
evaporation and thus have high vapour pressure.
iii. Effect addition of non-volatile solute
When a non-volatile solute is added to a pure solvent (liquid) temperature falls (as
heat is absorbed for dissolution) hence, vapour pressure also falls. Thus, vapour
pressure of a solution is less than its solvent (liquid).

Surface Tension
Surface Tension is the property of liquid due to which it has a tendency to have a
shape that has minimum surface area. Surface Tension can be described as force that
causes the surface of liquid to remain constant.

Molecules in liquid state attract one another. Consider molecule A, which lies entirely
inside the liquid is attracted equally on all sides and the net pull on the molecule is
zero. Now, consider the case of the molecule B at the surface is however different. It
is only partially surrounded by other molecules and there being no molecules above
it, it is subjected only to attractive forces of molecules below it. Molecule B, therefore,
experiences a net downward attractive force that is perpendicular to the plane of the
surface. This attractive force pulls as many molecules as possible from the surface to
the interior of the liquid and tends to make the surface area of the liquid as small as
possible.
The surface of the liquid, therefore, contracts and exhibits a state of tension. The
surface tension of a liquid is defined as the work (energy) required to expand the
surface of a liquid by unit area.

Viscosity
The flow is a characteristic property of liquids. Viscosity is defined as the internal
resistance of a liquid to flow. Liquid which flow slowly are solid to be more viscous than
the liquids which flow rapidly. Viscosity may be looked upon as the force of friction (F)
between two layers of a liquid moving past one another with different velocities.

Solutions
A solution is a homogeneous mixture of two or more substances having uniform
properties throughout. Thus, it is a single phase being homogeneous throughout. The
substances of which the solution is made are called components.
Solutions are generally two-components or binary systems consisting of solute which
is present in smaller quantity that is dissolved to form a solution, and solvent which is
present in larger quantity in which solute dissolves.

Page 2 of 15
 .
Solubility
The maximum amount of solute dissolved in 100 g of the solvent to form a saturated
solution at a particular temperature is called solubility. The extent to which one
substance (say solute) dissolves in another one (say solvent) to form a solution
(referred as solubility) depends upon the nature of the substance involved. Solubility
is influenced by temperature and pressure.
Solubility of gases in liquids
Gases are completely miscible with each other. Gases are soluble in liquids as well as
in solids. The solubility of a gas in liquid can be defined as the volume of the gas (in
cm’) which will dissolve in 1cm3 of the liquid to form a saturated solution at particular
temperature and pressure.
Generally, gases dissolve in liquid to form homogeneous solution. For example, Soda-
water contains CO, dissolved in water under high pressure.
Effect of temperature on solubility of gases in liquids
Generally, the solubility of gas decreases with increase in temperature because
dissolution of a gas is an exothermic process. But there are some exceptions like
solubility of H2 and inert gases increases slightly with increase temperature mainly in
non-aqueous solvents like ethanol,.
Effect of pressure on solubility of gases in liquids: Henrys Law
Solubility of a gas in a liquid also depends on the pressure as stated by Henry's law
"the solubility of a gas in a liquid is directly proportional to the pressure of the
gas".
If p is the partial pressure of the gas in solution and χ the mole fraction, then.

where, KH is Henry's law constant. Value of KH depends on the nature of the gas at
constant temperature.
For example to increase the solubility of CO, in soft drinks and soda water, the bottle
is sealed under high pressure. The higher the value of KH at a given pressure, the
lower is the solubility of the gas in the liquid. Thus KH, is the function the nature of the
gas. Different gases have different KH values at the given temperature.

Page 3 of 15
Some biological phenomena and applications explained on the basis of Henry's
law
(i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed
under high pressure..
(ii) High pressure exists in underwater that increases the solubility of atmospheric
gases like N2,O2, in blood of sea divers. When divers come towards surface, the
pressure gradually decreases due to which the dissolved gases are released. But due
to greater solubility, N2 will remain dissolved and form bubbles in the blood. These
bubbles affect nerve impulses and give rise a medical condition called bends. To
minimise the painful effects of bends, O2, diluted with less soluble helium gas is used
as breathing gas for sea or scuba divers.

Example (Henrysl law).

Henry's law constant of CO2 in water is 1.67 x 108 Pa at 298 K. Calculate the quantity
of CO2 in 500 mL soda water under 2.5 atm CO2 pressure at 298 K.

Assignment (Henry's law)

1. If N2 gas is bubbled through water at 293 K, how many millimoles of N 2 gas
would dissolve in 1 L of water. Assume that N2 exerts a partial pressure of 0.987
bar. Given, that Henry's law constant for N2 at 293 K is 76.48 kbar

Page 4 of 15
Colligative Properties
Properties which depend entirely upon the number of particles of solute contained in
a known volume of a given solvent and not all upon the nature (chemical composition
or constitution) of the solute are called colligative properties. These properties depend
on the nature of the solvent.

Boiling Point Elevation

If a non-volatile solute is added to the solvent, there is decrease in temperature due
to absorption of heat used in dissolution. Since, vapour pressure is dependent on
temperature there is a decrease in vapour-pressure of the solution and therefore,
vapour pressure of the solution becomes smaller than that of pure solvent.

Consequently, the temperature at which the vapour pressure of the solution

becomes equal to the atmospheric pressure will be greater than of pure solvent,
thus, boiling point of solution increases and hence, the boiling point (T) of the
solution is higher than that of the solvent (T o). It is called elevation in boiling
point, ∆Tb).

If To is the boiling point of the pure solvent corresponding to 1 atm at point and T is
the boiling point of the solution containing w1 grams of non-volatile solute (molar mass
= m1) in w2 g solvent, corresponding to 1 atm.
Therefore;

Where Kb, is the molal boiling point elevation constant (Ebullioscopic constant) and is
equal to elevation in boiling point when one mole of solute is dissolved in 1000 g
solvent. It is also related to boiling point of solvent (To) and latent heat of vaporisation
(∆Hv) by the equation.

Page 5 of 15
Example 3 (Boiling Point Elevation).

Freezing Point Depression

Freezing point (fp) of a liquid is defined as that temperature at which it is in equilibrium
with its solid slate. At freezing point of a solvent, liquid and solid states will have same
vapour pressure. Thus, freezing point is the temperature at which solid and liquid
states of a substance have same vapour pressure.

If a non-volatile solute is added to the solvent, there is decrease in vapour

pressure of the solution due to absorption of heat and thus the freezing point of
the solution (T) is less than that of pure solvent (T o). It is called depression in
freezing point, ∆Tf.

If To is the freezing point of the pure solvent corresponding to 1 atm at and T is the
freezing point of the solution containing w 1g1of non-volatile solute in of solvent
corresponding to 1 atm.

Page 6 of 15
Thus, molal freezing point depression constant is equal to depression in freezing point
of 1 molal solution (having 1 mole solute in 1 kg solvent). Kf is related to freezing point
(T0) and latent heat of fusion (∆Hf.) of the solvent by equation

Example (Freezing point depression)

Page 7 of 15
Osmosis and Osmotic Pressure
Spontaneous flow of solvent molecules from dilute solution (it may be pure solvent,
i.e. region of low concentration) into the concentrated solution (i.e. region of high
concentration) through a semi-permeable membrane is called osmosis. This process
continues till the concentration on both sides of the membrane becomes equal.

The osmotic pressure of a solution molecules is the excess pressure that must
be applied to the solution to prevent osmosis, i.e. to stop the passage of solvent
molecules through semi-permeable membrane into the solution.

Laws of osmotic pressure

Osmotic pressure of a solution depends on the concentration of solution, higher the
concentration higher the osmotic pressure.
So osmotic pressure is also a colligative property, van't Hoff through this study
concluded that a dilute solution becomes like an ideal gas, so ideal gas laws are also
applicable to dilute solution
.
(i) Boyle's-van't Hoff law . This states that at a constant temperature (isothermal
condition), the osmotic pressure (π) of a solution varies inversely as volume (V)
containing one mole of a solute. This relationship is very similar to Boyle's law for
gases , hence it Is called the Boyle—van't Hoff Law for dilute solutions.

(ii) Charles'-van't Hoff law This states that for given volume of solution, osmotic
pressure is directly proportional to temperature. This is similar to Charles' law for gases
and is known as charles'-van't Hoff law for dilute solutions.

(iii) van't Hoff theory for dilute solution By combining above two laws,

Page 8 of 15
Page 9 of 15
Page 10 of 15
Example (Osmotic pressure related to molar mass)

Raoult's law (Vapour-pressure lowering of solutions)

If a non-volatile solute is added to a solvent, temperature falls and thus vapour
pressure of the solution is lower than that of the pure solvent.
According to Raoult's law, the vapour pressure of a solution containing a non-
volatile solute is equal to the vapour pressure of pure solvent times the mole
fraction of the solvent.

Page 11 of 15
Page 12 of 15
Example (Vapour pressure of a mixture of non-volatile solute in liquid solvent)

Page 13 of 15
Example 6 (Molar Mass from Raoult’s Law)

Page 14 of 15
Azeotropic Mixtures
In case of positive and negative deviations, from Raoult's law the boiling point
composition curves have minima or maxima. The separation of such solutions into
their component can't be obtained by simple or fractional distillation and these are
called azeotropic mixture.
A binary mixture having similar composition in liquid and vapour phase and which boils
at a constant temperature and distils over without undergoing any change in its
composition is called Azeotrope. There are two types of azeotropes called as minimum
boiling azeotrope and maximum boiling azeotrope.
(i) Minimum boiling azeotropes comprises of non-ideal solution that shows positive
deviation from Raoult's law. e.g. solution of ethanol and water shows such a large
deviation from Raoult's law.
(ii) Maximum boiling azeotropes comprises of non-ideal solutions that shows
negative deviation from Raoult's law. e.g. HNO3 and H2O shows such a negative
deviation from Raoult's law .

Page 15 of 15